Mercaptosilane polymer mixture

ABSTRACT

The invention relates to mercaptosilane-polymer blends comprising at least one mercaptosilane of the general formula I 
     
       
         
         
             
             
         
       
     
     and at least one polymer selected from the group of polypropylene, polyethylene and ethylene-vinyl acetate. They are produced by mixing the mercaptosilane of the general formula I with the polymer. 
     They can be used in rubber mixtures.

The invention relates to a mercaptosilane-polymer blend, a process for production thereof, and also use of said blend.

In the tyre industry, sulphur silanes are sometimes used in order, in combination with silica, to improve rolling resistance, wet skid performance and abrasion resistance. The sulphur silanes normally used are liquid, and introduction of these therefore requires that the liquid silane be weighed out in advance to give portions sealed within a film or that liquid is metered directly into the mixer. In order to avoid this complicated mode of addition (most kneaders not having any liquid metering system), the sulphur silanes can be absorbed onto a carrier. The intention is that the carrier does not react with the sulphur silane, in order that the complete amount of silane is available within the tyre mixture.

EP 1285926, EP 1683801 and EP 1829922 disclose mercaptosilanes or polysulphidic silanes having polyether groups. The silanes can also have been absorbed on an organic carrier.

Furthermore, KR 850000081 discloses silane/filler blends and DE 102012205642 discloses mercaptosilane/carbon black blends.

U.S. Pat. No. 7,078,551 moreover discloses blocked mercaptosilanes on carrier.

Disadvantageous aspects of the known mercaptosilane/carrier blends are impairment of storage stability, of processability, of reinforcement performance, and of dynamic stiffness and/or dispersibility.

It is an object of the present invention to provide blends of mercaptosilanes with polymers which exhibit good storage stability and processability, good reinforcement performance, and good dynamic stiffness and dispersibility.

The invention provides a mercaptosilane-polymer blend, characterized in that this comprises at least one mercaptosilane of the general formula I

where R¹ is an alkyl polyether group —O—(R⁵—O)_(m)—R⁶, where R⁵ is identical or different and is a branched or unbranched, saturated or unsaturated, aliphatic divalent C1-C30 hydrocarbon group, preferably CH₂—CH₂, CH₂—CH(CH₃), —CH(CH₃)—CH₂— or CH₂—CH₂—CH₂, m is on average from 1 to 30, preferably from 2 to 20, particularly preferably from 2 to 15, very particularly preferably from 3 to 10, extremely preferably from 3.5 to 7.9, and R⁶ is composed of at least 1, preferably at least 11, particularly preferably at least 12, C atoms and is an unsubstituted or substituted, branched or unbranched monovalent alkyl, alkenyl, aryl or aralkyl group,

R² is identical or different and is an R¹, C1-C12-alkyl or R⁷O group, where R⁷ is H, methyl, ethyl, propyl, C9-C30 branched or unbranched monovalent alkyl, alkenyl, aryl, or aralkyl group or (R⁶)₃Si group, where R⁸ is C1-C30 branched or unbranched alkyl or alkenyl group,

R³ is a branched or unbranched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic/aromatic divalent C1-C30, preferably C1-C6, particularly preferably C3, hydrocarbon group and

R⁴ is H, CN or (C═O)—R⁹, where R⁹ is a branched or unbranched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic/aromatic monovalent C1-C30, preferably C5 to C30, particularly preferably C5 to C20, very particularly preferably C7 to C15, extremely preferably C7 to C11, hydrocarbon group,

and at least one polymer selected from the group of polypropylene, polyethylene, preferably HDPE, ethylene-vinyl acetate and mixtures of the abovementioned polymers.

The mercaptosilane-polymer blend can comprise at least 20% by weight, preferably at least 25% by weight, particularly preferably from 30% to 70% by weight, of mercaptosilane of the general formula I, based on the mercaptosilane-polymer blend.

The ratio by weight of mercaptosilane of the general formula I to polymer can be from 30:70 to 60:40, preferably from 40:60 to 50:50.

The molar mass of the polymer can be from 50 000-1 000 000 g/mol, preferably from 80 000 to 500 000 g/mol, particularly preferably from 100 000 to 250 000 g/mol (DIN EN ISO 16014-5: plastics—Determination of average molecular mass and molecular mass distribution of polymers using size-exclusion chromatography—Part 5: Method using light-scattering detection).

The melting point of the polymer can be from 80 to 200° C., preferably from 90 to 180° C. (Differential Scanning calorimetry—DSC Determination method, DIN EN ISO 11357). Very particularly preferred melting points can be: ethylene-vinyl acetate from 90 to 120° C., polyethylene from 105 to 140° C. and polypropylene from 140 to 175° C.

The bulk density of the polymer can be from 80 to 150 kg/m³, preferably from 90 to 140 kg/m³ (DIN EN ISO 60).

The melt volume flow rate (MFR) of the polymer can be from 0.2 to 30 g/10 min (ISO 1133: 190° C./2.16 kg). Particularly preferred melt volume flow rates can be: ethylene-vinyl acetate from 0.4 to 1.0 g/10 min, polyethylene from 1.0 to 5.0 g/10 min and polypropylene from 20 to 30 g/10 min.

The glass transition temperature of the polymer can be from −80 to +10° C. (ISO 1133). Particularly preferred glass transition temperatures can be: ethylene-vinyl acetate −30 to −10° C., polyethylene from −80 to −60° C. and polypropylene from −30 to +10° C.

The polyethylene polymer can be an HDPE. The density of the HDPE can be from 0.94 to 0.97 g/cm³.

The bulk density of the mercaptosilane-polymer blend can be from 80 to 900 kg/m³ (DIN EN ISO 60).

The polymer ethylene-vinyl acetate is a copolymer of vinyl acetate and ethylene and can comprise from 4 to 30% by weight, preferably from 4.3 to 6.7% by weight, of vinyl acetate (DIN EN ISO 4613-2: Plastics—Ethylene-vinyl acetate (E/VAC) moulding and extrusion materials—Part 2: Preparation of test specimens and determination of properties).

The mercaptosilanes of the general formula I can be compounds where R¹ is an alkyl polyether group —O—(R⁵—O)_(m)—R⁶, where R⁵ is identical or different and is a branched or unbranched, saturated or unsaturated, aliphatic divalent C1-C30 hydrocarbon group, m is on average from 1 to 30, and R⁶ is composed of at least 11 C atoms and is an unsubstituted or substituted, branched or unbranched monovalent alkyl, alkenyl, aryl or aralkyl group,

R² is identical and is a C1-C12-alkyl or R⁷O group, where R⁷ is H, ethyl, propyl, C9-C30 branched or unbranched monovalent alkyl, alkenyl, aryl, or aralkyl group or (R⁸)₃Si group, where R⁸ is C1-C30 branched or unbranched alkyl or alkenyl group,

R³ is a branched or unbranched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic/aromatic divalent C1-C30 hydrocarbon group and

R⁴ is H, CN or (C═O)—R⁹, where R⁹ is a branched or unbranched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic/aromatic monovalent C1-C30 hydrocarbon group.

The mercaptosilanes of the general formula I can be compounds where R¹ is —O—(C₂H₄—O)₅—C₁₁H₂₃, —O—(C₂H₄—O)₅—C₁₂H₂₅, —O—(C₂H₄—O)₅—C₁₃H₂₇, —O—(C₂H₄—O)₅—C₁₄H₂₉, —O—(C₂H₄—O)₅—C₁₅H₃₁, —O—(C₂H₄—O)₃—C₁₃H₂₇, —O—(C₂H₄—O)₄—C₁₃H₂₇, —O—(C₂H₄—O)₆—C₁₃H₂₇, —O—(C₂H₄—O)₇—C₁₃H₂₇, —O—(CH₂CH₂—O)₅—(CH₂)₁₀CH₃, —O—(CH₂CH₂—O)₅—(CH₂)₁₁CH₃, —O—(CH₂CH₂—O)₅—(CH₂)₁₂CH₃, —O—(CH₂CH₂—O)₅—(CH₂)₁₃CH₃, —O—(CH₂CH₂—O)₅—(CH₂)₁₄CH₃, —O—(CH₂CH₂—O)₃—(CH₂)₁₂CH₃, —O—(CH₂CH₂—O)₄—(CH₂)₁₂CH₃, —O—(CH₂CH₂—O)₆—(CH₂)₁₂CH₃, —O—(CH₂CH₂—O)₇—(CH₂)₁₂CH₃,

R² is different and is an R¹, C1-C12-alkyl or R⁷O group, where R⁷ is H, methyl, ethyl, propyl, C9-C30 branched or unbranched monovalent alkyl, alkenyl, aryl, or aralkyl group or (R⁸)₃Si group, where R⁸ is C1-C30 branched or unbranched alkyl or alkenyl group,

R³ is a branched or unbranched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic/aromatic divalent C1-C30 hydrocarbon group and

R⁴ is H, CN or (C═O)—R⁹, where R⁹ is a branched or unbranched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic/aromatic monovalent C1-C30 hydrocarbon group.

The mercaptosilanes of the general formula I can be compounds where R¹ is —O—(C₂H₄—O)₅—C₁₁H₂₃, —O—(C₂H₄—O)₅—C₁₂H₂₅, —O—(C₂H₄—O)₅—C₁₃H₂₇, —O—(C₂H₄—O)₅—C₁₄H₂₉, —O—(C₂H₄—O)₅—C₁₅H₃₁, —O—(C₂H₄—O)₃—C₁₃H₂₇, —O—(C₂H₄—O)₄—C₁₃H₂₇, —O—(C₂H₄—O)₆—C₁₃H₂₇, —O—(C₂H₄—O)₇—C₁₃H₇, —O—(CH₂CH₂—O)₅—(CH₂)₁₀CH₃, —O—(CH₂CH₂—O)₅—(CH₂)₁₁CH₃, —O—(CH₂CH₂—O)₅—(CH₂)₁₂CH₃, —O—(CH₂CH₂—O)₅—(CH₂)₁₃CH₃, —O—(CH₂CH₂—O)₅—(CH₂)₁₄CH₃, —O—(CH₂CH₂—O)₃—(CH₂)₁₂CH₃, —O—(CH₂CH₂—O)₄—(CH₂)₁₂CH₃, —O—(CH₂CH₂—O)₆—(CH₂)₁₂CH₃, —O—(CH₂CH₂—O)₇—(CH₂)₁₂CH₃,

R² is R¹ group,

R³ is a branched or unbranched, saturate or unsaturated, aliphatic, aromatic or mixed aliphatic/aromatic divalent C1-C30 hydrocarbon group and

R⁴ is H, CN or (C═O)—R⁹, where R⁹ is a branched or unbranched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic/aromatic monovalent C1-C30 hydrocarbon group.

Preferred compounds of the formula I where R⁴═H can be:

[(C₁₁H₂₃O—(CH₂—CH₂O)₂](EtO)₂Si(CH₂)₃SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₃](EtO)₂Si(CH₂)₃SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₄](EtO)₂Si(CH₂)₃SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₅](EtO)₂Si(CH₂)₃SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₆](EtO)₂Si(CH₂)₃SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₂](EtO)₂Si(CH₂)₃SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₃](EtO)₂Si(CH₂)₃SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₄](EtO)₂Si(CH₂)₃SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₅](EtO)₂Si(CH₂)₃SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₆](EtO)₂Si(CH₂)₃SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₂](EtO)₂Si(CH₂)₃SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₃](EtO)₂Si(CH₂)₃SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₄](EtO)₂Si(CH₂)₃SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₅](EtO)₂Si(CH₂)₃SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₆](EtO)₂Si(CH₂)₃SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₂](EtO)₂Si(CH₂)₃SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₃](EtO)₂Si(CH₂)₃SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₄](EtO)₂Si(CH₂)₃SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₅](EtO)₂Si(CH₂)₃SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₆](EtO)₂Si(CH₂)₃SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₂](EtO)₂Si(CH₂)₃SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₃](EtO)₂Si(CH₂)₃SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₄](EtO)₂Si(CH₂)₃SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₅](EtO)₂Si(CH₂)₃SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₆](EtO)₂Si(CH₂)₃SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₂](EtO)₂Si(CH₂)₃SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₃](EtO)₂Si(CH₂)₃SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₄](EtO)₂Si(CH₂)₃SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₅](EtO)₂Si(CH₂)₃SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₆](EtO)₂Si(CH₂)₃SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₂](EtO)₂Si(CH₂)₃SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₃](EtO)₂Si(CH₂)₃SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₄](EtO)₂Si(CH₂)₃SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₅](EtO)₂Si(CH₂)₃SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₆](EtO)₂Si(CH₂)₃SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₂]₂(EtO)Si(CH₂)₃SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₃]₂(EtO)Si(CH₂)₃SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₄]₂(EtO)Si(CH₂)₃SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₅]₂(EtO)Si(CH₂)₃SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₆]₂(EtO)Si(CH₂)₃SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₂]₂(EtO)Si(CH₂)₃SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₃]₂(EtO)Si(CH₂)₃SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₄]₂(EtO)Si(CH₂)₃SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₅]₂(EtO)Si(CH₂)₃SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₆]₂(EtO)Si(CH₂)₃SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₂]₂(EtO)Si(CH₂)₃SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₃]₂(EtO)Si(CH₂)₃SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₄]₂(EtO)Si(CH₂)₃SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₅]₂(EtO)Si(CH₂)₃SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₆]₂(EtO)Si(CH₂)₃SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₂]₂(EtO)Si(CH₂)₃SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₃]₂(EtO)Si(CH₂)₃SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₄]₂(EtO)Si(CH₂)₃SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₅]₂(EtO)Si(CH₂)₃SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₄]₂(EtO)Si(CH₂)₃SH,

[(C₁₅H₃₀—(CH₂—CH₂O)₂]₂(EtO)Si(CH₂)₃SH,

[(C₁₅H₃O—(CH—CH₂O)₃]₂(EtO)Si(CH₂)₃SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₄]₂(EtO)Si(CH₂)₃SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₅]₂(EtO)Si(CH₂)₃SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₄]₂(EtO)Si(CH₂)₃SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₂]₂(EtO)Si(CH₂)₃SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₃]₂(EtO)Si(CH₂)₃SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₄]₂(EtO)Si(CH₂)₃SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₅]₂(EtO)Si(CH₂)₃SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₆]₂(EtO)Si(CH₂)₃SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₂](EtO)Si(CH₂)₃SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₃]₂(EtO)Si(CH₂)₃SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₄]₂(EtO)Si(CH₂)₃SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₅]₂(EtO)Si(CH₂)₃SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₆]₂(EtO)Si(CH₂)₃SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₂]₃Si(CH₂)₃SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₃]₃Si(CH₂)₃SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₄]₃Si(CH₂)₃SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₅]₃Si(CH₂)₃SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₆]₃Si(CH₂)₃SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₂]₃Si(CH₂)₃SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₃]₃Si(CH₂)₃SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₄]₃Si(CH₂)₃SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₅]₃Si(CH₂)₃SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₆]₃Si(CH₂)₃SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₂]₃Si(CH₂)₃SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₃]₃Si(CH₂)₃SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₄]₃Si(CH₂)₃SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₅]₃Si(CH₂)₃SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₆]₃Si(CH₂)₃SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₂]₃Si(CH₂)₃SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₃]₃Si(CH₂)₃SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₄]₃Si(CH₂)₃SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₅]₃Si(CH₂)₃SH,

[(C₁₄H₂₉—(CH₂—CH₂O)₆]₃Si(CH₂)₃SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₂]₃Si(CH₂)₃SH,

[(C₁₅H₃₁—(CH₂—CH₂O)₃]₃Si(CH₂)₃SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₄]₃Si(CH₂)₃SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₅]₃Si(CH₂)₃SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₆]₃Si(CH₂)₃SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₂]₃Si(CH₂)₃SH,

[(C₁₆H₃₃—(CH₂—CH₂O)₃]₃Si(CH₂)₃SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₄]₃Si(CH₂)₃SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₅]₃Si(CH₂)₃SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₆]₃Si(CH₂)₃SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₂]₃Si(CH₂)₃SH,

[(C₁₇H₃₅—(CH₂—CH₂O)₃]₃Si(CH₂)₃SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₄]₃Si(CH₂)₃SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₅]₃Si(CH₂)₃SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₆]₃Si(CH₂)₃SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₂](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₃](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₄](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₅](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₆](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₂](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₃](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₄](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₅](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₆](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₂](EtO)₂Si—CH₂—CH(CH₃)—CH—SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₃](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₄](EtO)₂Si—CH_(z)—CH(CH₃)—CH₂—SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₅](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₆](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₂](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₃](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₄H₂₉O—(CH—CH₂O)₄](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₅](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₆](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₂](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₃](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₄](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₅](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₆](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₂](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₃](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₄](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₅](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₆](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₂](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₃](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₄](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₅](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₆](EtO)₂Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₂]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₃]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₄]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₅]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₆]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₂]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₃]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₄]₂(EtO)Si—CH_(z)—CH(CH₃)—CH₂—SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₅]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₆]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₃H₂₃—(CH₂—CH₂O)₂]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₃]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₃H₂₇—(CH₂—CH₂O)₄]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₅]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₆]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₂]₂(EtO)Si—CH₂—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₃]₂(EtO)Si—CH₂—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₄]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₅]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₆]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₂]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₃]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₄]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₅]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₆]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₂]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₃]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₄]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₅]₂(EtO)Si—H—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₆]₂(EtO)Si—H—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₂]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₃]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₄]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₅]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₆]₂(EtO)Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₂]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₃]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₄]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₅]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₁H₂₃O—(CH₂—CH₂O)₆]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₂]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₃]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₄]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₅]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₂H₂₅O—(CH₂—CH₂O)₆]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₂]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₃]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₄]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₅]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₃H₂₇O—(CH₂—CH₂O)₆]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₂]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₃]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₄]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₅]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₄H₂₉O—(CH₂—CH₂O)₆]₃Si—CH₂—CH(CH₃)—CH₂—SH.

[(C₁₅H₃₁O—(CH₂—CH₂O)₂]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₃]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₄]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₅]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₅H₃₁O—(CH₂—CH₂O)₆]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₂]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₃]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₄]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₅]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₆H₃₃O—(CH₂—CH₂O)₆]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₂]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₃]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₄]₃Si—CH₂—CH(CH₃)—CH₂—SH,

[(C₁₇H₃₅O—(CH₂—CH₂O)₅]₃Si—CH₂—CH(CH₃)—CH₂—SH or

[(C₁₇H₃₅O—(CH₂—CH₂O)₆]₃Si—CH₂—CH(CH₃)—CH₂—SH, where R⁶ can be branched or unbranched.

Preferred compounds of the formula I where R⁴═CN can be:

[(C₁₁H₂₃O—(CH₂—CH₂O)₂](EtO)₂Si(CH₂)₃SCN,

[(C₁₁H₂₃O—(CH₂—CH₂O)₃](EtO)₂Si(CH₂)₃SCN,

[(C₁₁H₂₃O—(CH₂—CH₂O)₄](EtO)₂Si(CH₂)₃SCN,

[(C₁₁H₂₃O—(CH₂—CH₂O)₅](EtO)₂Si(CH₂)₃SCN,

[(C₁₁H₂₃O—(CH₂—CH₂O)₆](EtO)₂Si(CH₂)₃SCN,

[(C₁₂H₂₅O—(CH₂—CH₂O)₂](EtO)₂Si(CH₂)₃SCN,

[(C₁₂H₂₅O—(CH₂—CH₂O)₃](EtO)₂Si(CH₂)₃SCN,

[(C₁₂H₂₅O—(CH₂—CH₂O)₄](EtO)₂Si(CH₂)₃SCN,

[(C₁₂H₂₅O—(CH₂—CH₂O)₅](EtO)₂Si(CH₂)₃SCN,

[(C₁₂H₂₅O—(CH₂—CH₂O)₆](EtO)₂Si(CH₂)₃SCN,

[(C₁₃H₂₇O—(CH₂—CH₂O)₂](EtO)₂Si(CH₂)₃SCN,

[(C₁₃H₂₇O—(CH₂—CH₂O)₃](EtO)₂Si(CH₂)₃SCN,

[(C₁₃H₂₇O—(CH₂—CH₂O)₄](EtO)₂Si(CH₂)₃SCN,

[(C₁₃H₂₇O—(CH₂—CH₂O)₅](EtO)₂Si(CH₂)₃SCN,

[(C₁₃H₂₇O—(CH₂—CH₂O)₆](EtO)₂Si(CH₂)₃SCN,

[(C₁₄H₂₉O—(CH₂—CH₂O)₂](EtO)₂Si(CH₂)₃SCN,

[(C₁₄H₂₉O—(CH₂—CH₂O)₃](EtO)₂Si(CH₂)₃SCN,

[(C₁₄H₂₉O—(CH₂—CH₂O)₄](EtO)₂Si(CH₂)₃SCN,

[(C₁₄H₂₉O—(CH₂—CH₂O)₅](EtO)₂Si(CH₂)₃SCN,

[(C₁₄H₂₉O—(CH₂—CH₂O)₆](EtO)₂Si(CH₂)₃SCN,

[(C₁₁H₂₃O—(CH₂—CH₂O)₂]₂(EtO)Si(CH₂)₃SCN,

[(C₁₁H₂₃O—(CH₂—CH₂O)₃]₂(EtO)Si(CH₂)₃SCN,

[(C₁₁H₂₃O—(CH₂—CH₂O)₄]₂(EtO)Si(CH₂)₃SCN,

[(C₁₁H₂₃O—(CH₂—CH₂O)₅]₂(EtO)Si(CH₂)₃SCN,

[(C₁₁H₂₃O—(CH₂—CH₂O)₆]₂(EtO)Si(CH₂)₃SCN,

[(C₁₂H₂₅O—(CH₂—CH₂O)₂]₂(EtO)Si(CH₂)₃SCN,

[(C₁₂H₂₅O—(CH₂—CH₂O)₃]₂(EtO)Si(CH₂)₃SCN,

[(C₁₂H₂₅O—(CH₂—CH₂O)₄]₂(EtO)Si(CH₂)₃SCN,

[(C₁₂H₂₅O—(CH₂—CH₂O)₅]₂(EtO)Si(CH₂)₃SCN,

[(C₁₂H₂₅O—(CH₂—CH₂O)₆]₂(EtO)Si(CH₂)₃SCN,

[(C₁₃H₂₇O—(CH₂—CH₂O)₂]₂(EtO)Si(CH₂)₃SCN,

[(C₁₃H₂₇O—(CH₂—CH₂O)₃]₂(EtO)Si(CH₂)₃SCN,

[(C₁₃H₂₇O—(CH₂—CH₂O)₄]₂(EtO)Si(CH₂)₃SCN,

[(C₁₃H₂₇O—(CH₂—CH₂O)₅]₂(EtO)Si(CH)₃SCN,

[(C₁₃H₂₇O—(CH₂—CH₂O)₆](EtO)Si(CH₂)₃SCN,

[(C₁₄H₂₉O—(CH₂—CH₂O)₂]₂(EtO)Si(CH₂)₃SCN,

[(C₁₄H₂₉O—(CH₂—CH₂O)₃]₂(EtO)Si(CH₂)₃SCN,

[(C₁₄H₂₉O—(CH₂—CH₂O)₄]₂(EtO)Si(CH₂)₃SCN,

[(C₁₄H₂₉O—(CH₂—CH₂O)₅]₂(EtO)Si(CH₂)₃SCN,

[(C₁₄H₂₉O—(CH₂—CH₂O)₆]₂(EtO)Si(CH₂)₃SCN,

[(C₁₁H₂₃O—(CH₂—CH₂O)₂]₃Si(CH₂)₃SCN,

[(C₁₁H₂₃O—(CH₂—CH₂O)₃]₃Si(CH₂)₃SCN,

[(C₁₁H₂₃O—(CH₂—CH₂O)₄]₃Si(CH₂)₃SCN,

[(C₁₁H₂₃O—(CH₂—CH₂O)₅]₃Si(CH₂)₃SCN,

[(C₁₁H₂₃O—(CH₂—CH₂O)₆]₃Si(CH₂)₃SCN,

[(C₁₂H₂₅O—(CH₂—CH₂O)₂]₃Si(CH₂)₃SCN,

[(C₁₂H₂₅O—(CH₂—CH₂O)₃]₃Si(CH₂)₃SCN,

[(C₁₂H₂₅O—(CH₂—CH₂O)₄]₃Si(CH₂)₃SCN,

[(C₁₂H₂₅O—(CH₂—CH₂O)₅]₃Si(CH₂)₃SCN,

[(C₁₂H₂₅O—(CH₂—CH₂O)₆]₃Si(CH₂)₃SCN,

[(C₁₃H₂₇O—(CH₂—CH₂O)₂]₃Si(CH₂)₃SCN,

[(C₁₃H₂₇O—(CH₂—CH₂O)₃]₃Si(CH₂)₃SCN,

[(C₁₃H₂₇O—(CH₂—CH₂O)₄]₃Si(CH₂)₃SCN,

[(C₁₃H₂₇O—(CH₂—CH₂O)₅]₃Si(CH₂)₃SCN,

[(C₁₃H₂₇O—(CH₂—CH₂O)₆]₃Si(CH₂)₃SCN,

[(C₁₄H₂₉O—(CH₂—CH₂O)₂]₃Si(CH₂)₃SCN,

[(C₁₄H₂₉O—(CH₂—CH₂O)₃]₃Si(CH₂)₃SCN,

[(C₁₄H₂₉O—(CH₂—CH₂O)₄]₃Si(CH₂)₃SCN,

[(C₁₄H₂₉O—(CH₂—CH₂O)₅]₃Si(CH₂)₃SCN or

[(C₁₄H₂₉O—(CH₂—CH₂O)₆]₃Si(CH₂)₃SCN, where R⁶ can be branched or unbranched.

Preferred compounds of the formula I where R⁴=—C(═O)—R⁹ and R⁹=branched or unbranched —C₅H₁₁, —C₆H₁₃, —C₇H₁₅, —C₈H₁₇, —C₉H₁₉, —C₁₀H₂₁, —C₁₁H₂₃, —C₁₂H₂₅, —C₁₃H₂₇, —C₁₄H₂₉, —C₁₅H₃₁, —C₁₆H₃₃, —C₁₇H₃₅ and —C₆H₅ (phenyl) can be:

[(C₁₁H₂₃O—(CH₂—CH₂O)₂](EtO)₂Si(CH₂)₃—C(═O)—R⁹,

[(C₁₁H₂₃O—(CH₂—CH₂O)₃](EtO)₂Si(CH₂)₃—C(═O)—R⁹,

[(C₁₁H₂₃—(CH₂—CH₂O)₄](EtO)₂Si(CH₂)₃—C(═O)—R⁹,

[(C₁₁H₂₃—(CH₂—CH₂O)₅](EtO)₂Si(CH₂)₃—C(═O)—R,

[(C₁₁H₂₃O—(CH₂—CH₂O)₆](EtO)₂Si(CH₂)₃—C(═O)—R,

[(C₁₂H₂₅O—(CH₂—CH₂O)₂](EtO)₂Si(CH₂)₃—C(═O)—R⁹,

[(C₁₂H₂₅O—(CH₂—CH₂O)₃](EtO)₂Si(CH₂)₃—C(═O)—R⁹,

[(C₁₂H₂₅O—(CH₂—CH₂O)₄](EtO)₂Si(CH₂)₃—C(═O)—R⁹,

[(C₁₂H₂₅O—(CH₂—CH₂O)₅](EtO)₂Si(CH₂)₃—C(═O)—R⁹,

[(C₁₂H₂₅O—(CH₂—CH₂O)₆](EtO)₂Si(CH₂)₃—C(═O)—R⁹,

[(C₁₃H₂₇O—(CH₂—CH₂O)₂](EtO)₂Si(CH₂)₃—C(═O)—R⁹,

[(C₁₃H₂₇O—(CH₂—CH₂O)₃](EtO)₂Si(CH₂)₃—C(═O)—R⁹,

[(C₁₃H₂₇O—(CH₂—CH₂O)₄](EtO)₂Si(CH₂)₃—C(═O)—R⁹,

[(C₁₃H₂₇O—(CH₂—CH₂O)₅](EtO)₂Si(CH₂)₃—C(═O)—R⁹,

[(C₁₃H₂₇O—(CH₂—CH₂O)₆](EtO)₂Si(CH₂)₃—C(═O)—R⁹,

[(C₁₄H₂₉O—(CH₂—CH₂O)₂](EtO)₂Si(CH₂)₃—C(═O)—R⁹,

[(C₁₄H₂₉O—(CH₂—CH₂O)₃](EtO)₂Si(CH₂)₃—C(═O)—R⁹,

[(C₁₄H₂₉O—(CH₂—CH₂O)₄](EtO)₂Si(CH₂)₃—C(═O)—R⁹,

[(C₁₄H₂₉O—(CH₂—CH₂O)₅](EtO)₂Si(CH₂)₃—C(═O)—R⁹,

[(C₁₄H₂₉O—(CH₂—CH₂O)₆](EtO)₂Si(CH₂)₃—C(═O)—R⁹,

[(C₁₁H₂₃O—(CH₂—CH₂O)₂]₂(EtO)Si(CH₂)₃—C(═O)—R⁹,

[(C₁₁H₂₃O—(CH₂—CH₂O)₃]₂(EtO)Si(CH₂)₃—C(═O)—R,

[(C₁₁CH₂₃O—(CH₂—CH₂O)₄]₂(EtO)Si(CH₂)₃—C(═O)—R⁹,

[(C₁₁CH₂₃O—(CH₂—CH₂O)₅]₂(EtO)Si(CH₂)₃—C(═O)—R⁹,

[(C₁₁H₂₃O—(CH₂—CH₂O)₆]₂(EtO)Si(CH₂)₃—C(═O)—R⁹,

[(C₁₂H₂₅O—(CH₂—CH₂O)₂]₂(EtO)Si(CH₂)₃—C(═O)—R⁹,

[(C₁₂H₂₅O—(CH₂—CH₂O)₃]₂(EtO)Si(CH₂)₃—C(═O)—R⁹,

[(C₁₂H₂₅O—(CH₂—CH₂O)₄]₂(EtO)Si(CH₂)₃—C(═O)—R⁹,

[(C₁₂H₂₅O—(CH₂—CH₂O)₅]₂(EtO)Si(CH₂)₃—C(═O)—R⁹,

[(C₁₂H₂₅O—(CH₂—CH₂O)₆]₂(EtO)Si(CH₂)₃—C(═O)—R⁹,

[(C₁₃H₂₇O—(CH₂—CH₂O)₂]₂(EtO)Si(CH₂)₃—C(═O)—R⁹,

[(C₁₃H₂₇O—(CH₂—CH₂O)₃]₂(EtO)Si(CH₂)₃—C(═O)—R⁹,

[(C₁₃H₂₇O—(CH₂—CH₂O)₄]₂(EtO)Si(CH₂)₃—C(═O)—R⁹,

[(C₁₃H₂₇O—(CH₂—CH₂O)₅]₂(EtO)Si(CH₂)₃—C(═O)—R⁹,

[(C₁₃H₂₇O—(CH₂—CH₂O)₆]₂(EtO)Si(CH₂)₃—C(═O)—R⁹,

[(C₁₄H₂₉O—(CH₂—CH₂O)₂]₂(EtO)Si(CH₂)₃—C(═O)—R⁹,

[(C₁₄H₂₉O—(CH₂—CH₂O)₃]₂(EtO)Si(CH₂)₃—C(═O)—R⁹,

[(C₁₄H₂₉O—(CH₂—CH₂O)₄]₂(EtO)Si(CH₂)₃—C(═O)—R⁹,

[(C₁₄H₂₉O—(CH₂—CH₂O)₅]₂(EtO)Si(CH₂)₃—C(═O)—R⁹,

[(C₁₄H₂₉O—(CH₂—CH₂O)₆]₂(EtO)Si(CH₂)₃—C(═O)—R⁹,

[(C₁₁H₂₃O—(CH₂—CH₂O)₂]₃Si(CH₂)₃—C(═O)—R⁹,

[(C₁₁H₂₃O—(CH₂—CH₂O)₃]₃Si(CH₂)₃—C(═O)—R⁹,

[(C₁₁H₂₃O—(CH₂—CH₂O)₄]₃Si(CH₂)₃—C(═O)—R⁹,

[(C₁₁H₂₃O—(CH₂—CH₂O)₅]₃Si(CH₂)₃—C(═O)—R⁹,

[(C₁₁H₂₃O—(CH₂—CH₂O)₆]₃Si(CH₂)₃—C(═O)—R⁹,

[(C₁₂H₂₅O—(CH₂—CH₂O)₂]₃Si(CH₂)₃—C(═O)—R⁹,

[(C₁₂H₂₅O—(CH₂—CH₂O)₃]₃Si(CH₂)₃—C(═O)—R⁹,

[(C₁₂H₂₅O—(CH₂—CH₂O)₄]₃Si(CH₂)₃—C(═O)—R⁹,

[(C₁₂H₂₅O—(CH₂—CH₂O)₅]₃Si(CH₂)₃—C(═O)—R⁹,

[(C₁₂H₂₅O—(CH₂—CH₂O)₆]₃Si(CH₂)₃—C(═O)—R⁹,

[(C₁₃H₂₇O—(CH₂—CH₂O)₂]₃Si(CH₂)₃—C(═O)—R⁹,

[(C₁₃H₂₇O—(CH₂—CH₂O)₃]₃Si(CH₂)₃—C(═O)—R⁹,

[(C₁₃H₂₇O—(CH₂—CH₂O)₄]₃Si(CH₂)₃—C(═O)—R⁹,

[(C₁₃H₂₇O—(CH₂—CH₂O)₅]₃Si(CH₂)₃—C(═O)—R⁹,

[(C₁₃H₂₇O—(CH₂—CH₂O)₆]₃Si(CH)₃—C(═O)—R⁹,

[(C₁₄H₂₉O—(CH₂—CH₂O)₂]₃Si(CH₂)₃—C(═O)—R⁹,

[(C₁₄H₂₉O—(CH₂—CH₂O)₃]₃Si(CH₂)₃—C(═O)—R⁹,

[(C₁₄H₂₉O—(CH₂—CH₂O)₄]₃Si(CH₂)₃—C(═O)—R⁹,

[(C₁₄H₂₉O—(CH₂—CH₂O)₅]₃Si(CH₂)₃—C(═O)—R⁹ or

[(C₁₄H₂₉O—(CH₂—CH₂O)₆]₃Si(CH₂)₃—C(═O)—R⁹

R⁶ can preferably be C₁₂ to C₁₇, very particularly preferably C₁₂ to C₁₆, extremely preferably C₁₂ to C₁₄, unsubstituted or substituted, branched or unbranched monovalent alkyl.

R⁶ can be a —C₁₁H₂₃, —C₁₂H₂₅, —C₁₃H₂₇, —C₁₄H₂₉, —C₁₅H₃₁, —C₁₆H₃₃ or —C₁₇H₃₅ alkyl group.

R⁶ can preferably be C₁₁ to C₃₅, particularly preferably C₁₁ to C₃₀, very particularly preferably C₁₂ to C₃₀, extremely preferably C₁₃ to C₂₀, unsubstituted or substituted, branched or unbranched monovalent alkenyl.

R⁶ can preferably be C₁₁ to C₁₄ and/or C₁₆ to C₃₀, very particularly preferably C₁₁ to C₁₄ and/or C₁₆ to C₂₅, extremely preferably C₁₂ to C₁₄ and/or C₁₆ to C₂₀, unsubstituted or substituted, branched or unbranched monovalent aralkyl.

R⁶ can, as alkenyl be C₁₁H₂₁, —C₁₂H₂₃, —C₁₃H₂₅, —C₁₄H₂₇, —C₁₅H₂₉, —C₁₆H₃₁ or —C₁₇H₃₃.

R¹ can be an alkoxylated castor oil (e.g. CAS 61791-12-6).

R¹ can be an alkoxylated oleyl amine (e.g. CAS 26635-93-8).

The polyether group (R⁵O)_(m) can comprise random units of ethylene and propylene oxide or polyether blocks made of polyethylene oxide and polypropylene oxide.

The polyether group (R⁵—O)_(m) can preferably be:

(—O—CH₂—CH₂—)_(a),

(—O—CH(CH₃)—CH₂—)_(a)

(—O—CH₂—CH(CH₃)—)_(a),

(—O—CH₂—CH₂—)_(a)(—O—CH(CH₃)—CH₂—),

(—O—CH₂—CH₂—) (—O—CH(CH₃)—CH₂—)_(a),

(—O—CH₂—CH₂—)_(a)(—O—CH₂—CH(CH₃)—),

(—O—CH₂—CH₂—)(—O—CH₂—CH(CH₃)—)_(a),

(—O—CH(CH₃)—CH₂—)_(a)(—O—CH₂—CH(CH₃)—),

(—O—CH(CH₃)—CH₂—)(—O—CH₂—CH(CH₃)—)_(a),

(—O—CH₂—CH₂—)_(a)(—O—CH(CH₃)—CH₂—)_(b)(—O—CH₂—CH(CH₃)—)_(c) or a combination of these,

where a, b and c are mutually independent and

a is from 1 to 50, preferably from 2 to 30, particularly preferably from 3 to 20, very particularly preferably from 4 to 15, extremely preferably from 5 to 12,

b is from 1 to 50, preferably from 2 to 30, particularly preferably from 3 to 20, very particularly preferably from 4 to 15, extremely preferably from 5 to 12 and

c is from 1 to 50, preferably from 2 to 30, particularly preferably from 3 to 20, very particularly preferably from 4 to 15, extremely preferably from 5 to 12.

The indices a, b and c are integers and denote the number of the repeating units.

When R⁴ is —H, —CN or —C(═O)—R⁹, the group (R⁵—O)_(m) can preferably comprise ethylene oxide units (CH₂—CH₂—O)_(a) or propylene oxide units (CH(CH₃)—CH₂—O)_(a) or (CH₂—CH(CH₃)—O)_(a).

When R⁴ is —H, —CN or —C(═O)—R⁹, the group (R⁵—O)_(m) can preferably comprise the following randomly distributed or in blocks: ethylene oxide units (CH₂—CH₂—O)_(a) or propylene oxide units (CH(CH₃)—CH₂—O)_(a) or (CH₂—CH(CH₃)—O)_(a).

When R⁴ is —H, the alkyl polyether group (R⁵—O)_(m) can preferably comprise the following randomly distributed or in blocks: ethylene oxide units (CH₂—CH₂—O)_(a) or propylene oxide units (CH(CH₃)—CH₂—O)_(a) or (CH₂—CH(CH₃)—O)_(a).

When R⁴ is —H, the group (R⁵—O)_(m) can preferably comprise propylene oxide units (CH(CH₃)—CH₂—O)_(a) or (CH₂—CH(CH₃)—O)_(a).

When R⁴ is —H, —CN or —C(C═O)—R⁹, the alkyl polyether group O—(R⁵—O)_(m)—R⁶ can be:

O—(CH₂—CH₂O)₂—C₁₁H₂₃, O—(CH₂—CH₂O)₃—C₁₁H₂₃, O—(CH₂—CH₂O)₄—C₁₁H₂₃, O—(CH₂—CH₂O)₅—C₁₁H₂₃, O—(CH₂—CH₂O)₆—C₁₁H₂₃, O—(CH₂—CH₂O)₇—C₁₁H₂₃,

O—(CH(CH₃)—CH₂O)₂—C₁₁H₂₃, O—(CH(CH₃)—CH₂O)₃—C₁₁H₂₃, O—(CH(CH₃)—CH₂O)₄—C₁₁H₂₃, O—(CH(CH₃)—CH₂O)₅—C₁₁H₂₃, O—(CH(CH₃)—CH₂O)₆—C₁H₂₃, O—(CH(CH₃)—CH₂O)₇—C₁₁H₂₃,

O—(CH₂—CH₂O)₂—C₁₂H₂₅, O—(CH₂—CH₂O)₃—C₁₂H₂₅, O—(CH₂—CH₂O)₄—C₁₂H₂₅, O—(CH₂—CH₂O)₅—C₁₂H₂₅, O—(CH₂—CH₂O)₆—C₁₂H₂₅, O—(CH₂—CH₂O)₇—C₁₂H₂₅,

O—(CH(CH₃)—CH₂O)₂—C₁₂H₂₅, O—(CH(CH₃)—CH₂O)₃—C₁₂H₂₅, O—(CH(CH₃)—CH₂O)₄—C₁₂H₂₅, O—(CH(CH₃)—CH₂O)₅—C₁₂H₂₅, O—(CH(CH₃)—CH₂O)₆—C₁₂H₂₅, O—(CH(CH₃)—CH₂O)₇—C₁₂H₂₅,

O—(CH₂—CH₂O)₂—C₁₃H₂₇, O—(CH₂—CH₂O)₃—C₁₃H₂₇, O—(CH₂—CH₂O)₄—C₁₃H₂₇, O—(CH₂—CH₂O)₅—C₁₃H₂₇, O—(CH₂—CH₂O)₆—C₁₃H₂₇, O—(CH₂—CH₂O)₇—C₁₃H₂₇,

O—(CH(CH₃)—CH₂O)₂—C₁₃H₂₇, O—(CH(CH₃)—CH₂O)₃—C₁₃H₂₇, O—(CH(CH₃)—CH₂O)₄—C₁₃H₂₇, O—(CH(CH₃)—CH₂O)₅—C₃H₂₇, O—(CH(CH₃)—CH₂O)₆—C₁₃H₂₇, O—(CH(CH₃)—CH₂O)—C₁₃H₂₇,

O—(CH₂—CH₂O)₂—C₁₄H₂₉, O—(CH₂—CH₂O)₃—C₁₄H₂₉, O—(CH₂—CH₂O)₄—C₁₄H₂₉, O—(CH₂—CH₂O)₅—C₁₄H₂₉, O—(CH₂—CH₂O)₆—C₁₄H₂₉, O—(CH₂—CH₂O)₇—C₁₄H₂₉,

O—(CH(CH₃)—CH₂O)₂—C₁₄H₂₉, O—(CH(CH₃)—CH₂O)₃—C₁₄H₂₉, O—(CH(CH₃)—CH₂O)₄—C₁₄H₂₉, O—(CH(CH₃)—CH₂O)₅—C₄H₂₉, O—(CH(CH₃)—CH₂O)₆—C₁₄H₂₉, O—(CH(CH₃)—H₂)₇—C₁₄H₂₉,

O—(CH₂—CH₂O)₂—C₁₅H₃₁, —(CH₂—CH₂O)₃—C₁₅H₃₁, O—(CH₂—CH₂O)₄—C₁₅H₃₁, O—(CH₂—CH₂O)₅—C₁₅H₃₁, O—(CH₂—CH₂O)₆—C₁₅H₃₁, O—(CH₂—CH₂O)₇—C₁₅H₃₁,

O—(CH(CH₃)—CH₂O)₂—C₁₅H₃₁, O—(CH(CH₃)—CH₂O)₃—C₁₅H₃₁, O—(CH(CH₃)—CH₂O)₄—C₁₅H₃₁, O—(CH(CH₃)—CH₂O)₅—C₅H₃₁, O—(CH(CH₃)—CH₂O)₆—C₅H₃₁, O—(CH(CH₃)—CH₂O)₇—C₁₅H₃₁,

O—(CH₂—CH₂O)₂—C₁₆H₃₃, O—(CH₂—CH₂O)₃—C₁₆H₃₃, O—(CH₂—CH₂O)₄—C₁₆H₃₃, O—(CH₂—CH₂O)₅—C₁₆H₃₃, O—(CH₂—CH₂O)₆—C₁₆H₃₃, O—(CH₂—CH₂O)₇—C₁₆H₃₃,

O—(CH(CH₃)—CH₂O)₂—C₁₆H₃₃, O—(CH(CH₃)—CHO)₃—C₁₆H₃₃, O—(CH(CH₃)—CH₂O)₄—C₁₆H₃₃, O—(CH(CH₃)—CH₂O)₅—C₁₆H₃₃, O—(CH(CH₃)—CH₂O)₆—C₁₆H₃₃, O—(CH(CH₃)—CH₂O)₇—C₁₆H₃₃,

O—(CH₂—CH₂O)₂—C₁₇H₃₅, O—(CH₂—CH₂O)₃—C₁₇H₃₅, O—(CH₂—CH₂O)₄—C₁₇H₃₅, O—(CH₂—CH₂O)₅—C₁₇H₃₅, O—(CH₂—CH₂O)₆—C₁₇H₃₅, O—(CH₂—CH₂O)₇—C₁₇H₃₅,

O—(CH(CH₃)—CH₂O)₂—C₁₇H₃₅, O—(CH(CH₃)—CH₂O)₃—C₁₇H₃₅, O—(CH(CH₃)—CH₂O)₄—C₁₇H₃₅, O—(CH(CH₃)—CH₂O)₅—C₁₇H₃₅, O—(H(CH₃)—CH₂O)₆—C₇H₃ or O—(CH(CH₃)—CH₂O)₇—C₁₇H₃₅.

The group R⁵ can have substitution. The group R⁶ can be C₁₃H₂₇.

R¹ can be —O—(C₂H₄—O)₅—C₁₁H₂₃, —O—(C₂H₄—O)₅—C₁₂H₂₅, —O—(C₂H₄—O)₅—C₁₃H₂₇, —O—(C₂H₄—O)₅—C₁₄H₂₉, —O—(C₂H₄—O)₅—C₁₅H₃₁, —O—(C₂H₄—O)₃—C₁₃H₂₇—O—(C₂H₄—O)₄—C₁₃H₂₇, —O—(C₂H₄—O)₆—C₃H₂₇, —O—(C₂H₄—O)₇—C₁₃H₂₇, —O—(CH₂CH₂—O)₅—(CH₂)₁₀CH₃, —O—(CH₂CH₂—O)—(CH₂)₁₁CH₃, —O—(CH₂CH₂—O)—(CH₂)₁₂CH₃, —O—(CH₂CH₂—O)—(CH₂)₁₃CH₃, —O—(CH₂CH₂—O)₅—(CH₂)₁₄CH₃, —O—(CH₂CH₂—O)₃—(CH₂)₁₂CH₃, —O—(CH₂CH₂—O)₄—(CH₂)₁₂CH₃, —O—(CH₂CH₂—O)₆—(CH₂)₁₂CH₃, —O—(CH₂CH₂—O)—(CH)₁₂CH₃,

The average branching number of the carbon chain R⁶ can be from 1 to 5, preferably from 1.2 to 4. The average branching number here is defined as the number of CH₃ groups minus 1.

R³ can be CH₂, CH₂CH₂, CH₂CH₂CH₂, CH₂CH₂CH₂CH₂, CH(CH₃), CH₂CH(CH₃), CH(CH₃)CH₂, C(CH₃)₂, CH(C₂H₅), CH₂CH₂CH(CH₃), CH₂CH(CH₃)CH₂

or

The mercaptosilane-polymer blend can comprise a mixture of different mercaptosilanes of the general formula I and optionally of condensates of these.

The mixture of different mercaptosilanes of the general formula I can comprise mercaptosilanes of the general formula I having various m values.

The mixture of different mercaptosilanes of the general formula I can comprise mercaptosilanes of the general formula I having various R⁶ groups. The R⁶ groups here can have different C-atom-chain lengths.

The mixture of different mercaptosilanes of the general formula I can comprise different mercaptosilanes of the general formula I having various R¹ and R² groups where the R¹ and R² groups are composed of alkoxy and alkyl polyether groups.

The mixture of different mercaptosilanes of the general formula I can comprise different mercaptosilanes of the general formula I having different R².

The mixture of different mercaptosilanes of the general formula I can comprise different mercaptosilanes of the general formula I having various R¹ and R² groups where the R¹ groups are composed of alkyl polyether groups and the R groups are composed of ethoxy groups and R⁶ has an alkyl-chain length of 13 C atoms, R⁵ is ethylene and m is on average 5.

The mixture of different mercaptosilanes of the general formula I can comprise different mercaptosilanes of the general formula I where R² is identical or different and is an ethoxy or alkyl polyether group (R¹), R⁶ has an alkyl-chain length of 13 C atoms, R⁵ is ethylene and m is on average 5, and R² is different.

The mixture of different mercaptosilanes of the general formula I can comprise different mercaptosilanes of the general formula I where R¹ and R² are alkoxy and alkyl polyether groups and R⁶ is composed of different C-atom-chain lengths.

The mixture of different mercaptosilanes of the general formula I can comprise different mercaptosilanes of the general formula I where R² is identical or different and is an alkoxy or alkyl polyether group (R¹), and R² in the mixture is different, and R⁶ is composed of different C-atom-chain lengths.

The mixture of different mercaptosilanes of the general formula I can preferably comprise

and optionally products of the hydrolysis and/or condensation of the abovementioned compounds.

From the mercaptosilanes of the formula I it is easily possible via water addition and optionally additive addition to form condensates, i.e. oligo- and polysiloxanes.

These oligomeric or polymeric siloxanes of the compounds of the formula I can be used as coupling reagents for the same applications as the monomeric compounds of the formula I.

The mercaptosilane compounds can also take the form of mixture of the oligomeric or polymeric siloxanes of mercaptosilanes of the general formula I or take the form of mixtures of mercaptosilanes of the general formula I with mixtures of the oligomeric or polymeric siloxanes of mercaptosilanes of the general formula I.

The invention further provides a process for the production of the mercaptosilane-polymer blend of the invention, where the process is characterized in that at least one mercaptosilane of the general formula I is mixed with at least one polymer selected from the group of polypropylene, polyethylene, ethylene-vinyl acetate and mixtures of the abovementioned polymers.

The process of the invention can be carried out continuously or batchwise.

The ratio by weight of mercaptosilane of the general formula I to polymer can be from 30:70 to 60:40, preferably from 40:60 to 50:50.

The process of the invention can be carried out at temperatures of from 5 to 150° C., preferably from 10 to 100° C., particularly preferably from 15 to 60° C. In order to avoid condensation reactions, it can be advantageous to carry out the reaction in an anhydrous environment, ideally under inert gas.

The process of the invention can be carried out at atmospheric pressure or at reduced pressure.

The mixing process in the process of the invention can use mechanical mixers. The mechanical mixers can firstly achieve uniform movement and mixing of product and can secondly avoid any excessive destruction of the granulated carrier material.

A parameter frequently used for the classification of solids mixers here is the Froude number (Fr), which gives the ratio of centrifugal acceleration to gravitational acceleration.

It is possible to use not only low-speed mixers where Fr<1, for example tumbling mixers or displacement mixers, but also high-speed mixers where Fr>1, for example impeller mixers, and also centrifugal mixers where Fr>>1.

Examples of a low-speed displacement mixer that can be used are drum mixers (for example from Engelsmann) and twin-shaft mixers (for example from Gericke or Forberg). Examples of high-speed mixers that can be used for the region where Fr>1 are ploughshare mixers (for example from Lödige) and vertical twin-shaft mixers (for example from Amixon). In the region where Fr>>1 it is possible to use centrifugal or intensive mixers (for example from Eirich or Mixaco).

Ploughshare mixers can particularly preferably be used for the process of the invention.

The mercaptosilane-polymer blend of the invention can be used as coupling agent between inorganic materials, for example glass fibres, metals, oxidic fillers, or silicas, and organic polymers, for example thermosets, thermoplastics or elastomers, or as crosslinking agent and surface modifier. The mercaptosilane-polymer blend of the invention can be used as coupling reagent in rubber mixtures, for example tyre treads.

The invention further provides a rubber mixture comprising

(A) at least one rubber,

(B) at least one filler, preferably precipitated silica, and

(C) at least one mercaptosilane-polymer blend of the invention.

Rubber used can be natural rubber and/or synthetic rubbers. Preferred synthetic rubbers are described by way of example in W. Hofmann, Kautschuktechnologie [Rubber Technology], Genter Verlag, Stuttgart 1980. They can be inter alia

-   -   polybutadiene (BR),     -   polyisoprene (IR),     -   styrene/butadiene copolymers, for example emulsion SBR (E-SBR)         or solution SBR (S-SBR), preferably having styrene contents of         from 1 to 60% by weight, particularly from 5 to 50% by weight         (SBR),     -   chloroprene (CR)     -   isobutylene/isoprene copolymers (IIR),     -   butadiene/acrylonitrile copolymers having acrylonitrile contents         of from 5 to 60% by weight, preferably from 10 to 50% by weight         (NBR),     -   partially hydrogenated or fully hydrogenated NBR rubber (HNBR)     -   ethylene/propylene/diene copolymers (EPDM)     -   abovementioned rubbers which also have functional groups, e.g.         carboxy, silanol or epoxy groups, for example epoxidized NR,         carboxy-functionalized NBR or silanol (—SiOH)- or siloxy         (—Si—OR)-functionalized SBR, or else a mixture of these rubbers.

In a preferred embodiment, the rubbers can be sulphur-vulcanizable. For the production of car tyre treads it is in particular possible to use anionically polymerized S-SBR rubbers (solution SBR) with a glass transition temperature above −50° C., and also mixtures of these with diene rubbers. It is particularly preferably possible to use S-SBR rubbers whose butadiene portion has more than 20% by weight vinyl fraction. It is very particularly preferably possible to use S-SBR rubbers whose butadiene portion has more than 50% by weight vinyl fraction.

It is preferably possible to use mixtures of the abovementioned rubbers which have more than 50% by weight, particularly more than 60% by weight, S-SBR content.

The following fillers can be used as fillers for the rubber mixture of the invention:

-   -   Carbon blacks: the carbon blacks to be used here are produced by         the lamp-black process, furnace-black process, gas-black process         or thermal process and have BET surface areas of from 20 to 200         m²/g. The carbon blacks can optionally also comprise         heteroatoms, for example Si.     -   Amorphous silicas produced for example by precipitation from         solutions of silicates or flame-hydrolysis of silicon halides         with specific surface areas of from 5 to 1000 m²/g, preferably         from 20 to 400 m²/g (BET surface area) and with primary particle         sizes of from to 400 nm. The silicas can optionally also take         the form of mixed oxides with other metal oxides, such as Al,         Mg, Ca, Ba, Zn and titanium oxides.     -   Synthetic silicates such as aluminium silicate, alkaline earth         metal silicates such as magnesium silicate or calcium silicate,         with BET surface areas of from 20 to 400 m²/g and primary         particle diameters of from 10 to 400 nm.     -   Synthetic or natural aluminium oxides and synthetic or natural         aluminium hydroxides.     -   Natural silicates such as kaolin and other naturally occurring         silicas.     -   Glass fibre and glass fibre products (mats, strands) or glass         microspheres.

It is preferably possible to use amounts of from 5 to 150 parts by weight, based in each case on 100 parts of rubber, of amorphous silicas produced by precipitation from solutions of silicates, with BET surface areas of from 20 to 400 m²/g, particularly from 100 m²/g to 250 m²/g.

The filler mentioned can be used alone or in a mixture.

The rubber mixture can comprise from 5 to 150 parts by weight of filler (B) and from 0.1 to 35 parts by weight, preferably from 2 to 20 parts by weight, particularly preferably from 5 to 15 parts by weight, of mercaptosilane-polymer blend (C) of the invention, where the parts by weight are based on 100 parts by weight of rubber.

The rubber mixture can also comprise silicone oil and/or alkylsilane.

The rubber mixture of the invention can comprise other known rubber auxiliaries, e.g. crosslinking agents, vulcanization accelerators, reaction accelerators, reaction retarders, antioxidants, stabilizers, processing aids, plasticizers, waxes or metal oxides, and also optionally activators such as triethanolamine, polyethylene glycol or hexanetriol.

The amounts that can be used of the rubber auxiliaries are conventional, depending inter alia on the intended use.

Conventional amounts can by way of example be amounts of from 0.1 to 50% by weight, based on rubber.

Sulphur or organic sulphur donors can be used as crosslinking agents.

The rubber mixture of the invention can comprise other vulcanization accelerators. Examples of suitable vulcanization accelerators that can be used are mercaptobenzothiazoles, sulphenamides, guanidines, dithio-carbamates, thioureas, thiocarbonates, and also zinc salts of these, for example zinc dibutyldithiocarbamate.

The rubber mixture of the invention can preferably also comprise

(D) a thiuram sulphide accelerator and/or carbamate accelerator and/or the corresponding zinc salts,

(E) a nitrogen-containing Co-activator,

(F) optionally other rubber auxiliaries and

(G) optionally other accelerators,

where the ratio by weight of accelerator (D) to nitrogen-containing Co-activator (E) is equal to or greater than 1.

The rubber mixture of the invention can comprise at least 0.25 part by weight, based on 100 parts by weight of rubber, of (D) tetrabenzylthiuram disulphide or tetramethylthiuram disulphide, at most 0.25 part by weight, based on 100 parts by weight of rubber, of (E) diphenylguanidine, and more parts by weight than (D) of (G) cyclohexyl- or dicyclohexylsulphenamide.

It is preferably possible to use sulphenamides together with guanidines and thiurams, particularly cyclohexylsulphenamide or dicylohexylsulphenamide together with diphenylguanidine and tetrabenzylthiuram disulphide or tetramethylthiuram disulphide.

Amounts that can be used of the vulcanization accelerators and sulphur are from 0.1 to 10% by weight, preferably from 0.1 to 5% by weight, based on the rubber used. It is particularly preferably possible to use amounts of from 1 to 4% by weight of sulphur and sulphenamides, amounts of from 0.2 to 1% by weight of thiurams and amounts of from 0% by weight to 0.5% by weight of guanidines.

The invention further provides a process for the production of the rubber mixture of the invention, where said process is characterized in that at least one rubber (A), at least one filler (B), at least one mercaptosilane-polymer blend (C) of the invention and optionally other rubber auxiliaries are mixed in a mixing assembly.

The blending of the rubbers with the filler and optionally rubber auxiliaries and with the mercaptosilane-polymer blend of the invention can be carried out in or on conventional mixing assemblies, such as rolls, internal mixers and mixing extruders. Rubber mixtures of this type can usually be produced in internal mixers, by first incorporating the rubbers, the filler, the mercaptosilane-polymer blend of the invention and the rubber auxiliaries by mixing at from 100 to 170° C., in one or more sequential thermomechanical mixing stages. The addition sequence and the juncture of addition of the individual components here can have a decisive effect on the resultant properties of the mixture. It is usually possible to admix the crosslinking chemicals with the resultant rubber mixture in an internal mixer or on a roll at from 40 to 110° C. and to process the mixture to give what is known as the crude mixture for the subsequent steps of the process, for example shaping and vulcanization.

The rubber mixture of the invention can be vulcanized at temperatures of from 80 to 200° C., preferably from 130 to 180° C., optionally under a pressure of from 10 to 200 bar.

The rubber mixture of the invention can be used for the production of mouldings, for example for the production of pneumatic and other tyres, tyre treads, cable sheathing, hoses, drive belts, conveyor belts, roll coverings, shoe soles, sealing elements, such as sealing rings and damping elements.

The invention further provides mouldings obtainable from the rubber mixture of the invention by vulcanization.

The mercaptosilane-polymer blends of the invention have the advantage that the mercaptosilane does not undergo any alteration even during a prolonged storage time.

Another advantage is good processability, good reinforcement performance, and good dynamic stiffness and dispersibility.

EXAMPLES Example 1

The polymer is dried for 8 hours at 26° C. and 80 mbar in a vacuum drying oven. The polymer is then weighed directly into a Somakon MP-L mechanical mixer (Somakon Verfahrenstechnik UG) and mixed at a rotation rate of 250 rpm and room temperature (Table 1), in such a way that the material rises up the outer wall. The scraper is set to a constant rotation rate of 30 rpm. The corresponding silane is applied dropwise by way of a 1.5 mm nozzle to the granulated materials by using a rotary piston pump. The metering rate varies from 7 to 7.5 g/min. The resultant product is post-treated overnight at room temperature in vacuo (50 mbar).

TABLE 1 Blend 1 Blend 2 Blend 3 Blend 4 Comparative Inventive Inventive Inventive ex. ex. ex. ex. Silane Si 363 Si 363 Si 363 Si 363 Amount of 158 g 105 g 158 g 210 g silane Polymer XP-712 XP 500 MP-100 XP-200 (nylon-12) (EVA) (PP) (HDPE) Amount of 105 g 160 g 104 g 140 g polymer Mixer 250 rpm 250 rpm 250 rpm 250 rpm rotation rate

Accurel XP-712 is a nylon-12 from Membrana GmbH.

Accurel XP-500 is an ethylene-vinyl acetate from Membrana GmbH.

Accurel MP-100 is a polypropylene from Membrana GmbH.

Accurel XP-200 is a HDPE from Membrana GmbH.

Si 363 is an organosilane of the formula Si(OR)₃(CH₂)₃—SH,

where R═C₂H₅ or alkyl polyether from Evonik Industries AG.

Example 2

The formulation used for the rubber mixtures is stated in Table 2 below. The unit phr here means proportions by weight, based on 100 parts of the crude rubber used. The amounts used of the mercaptosilane-polymer blends are isomolar, based on the mercaptosilane. The mixtures are produced at a batch temperature of 155° C. in a 1.5 l mixer (E-type).

TABLE 2 Amount [phr] Amount [phr] of Amount [phr] of Amount [phr] of Amount [phr] of reference rubber mixture I rubber mixture II rubber mixture III of reference rubber mixture of the invention, of the invention, of the invention, rubber mixture II, comprising comprising blend 2 comprising blend 3 comprising blend 4 Substance I “in situ” blend 1 of the invention of the invention of the invention 1^(st) stage Buna VSL 96 96 96 96 96 5025-2 Buna CB 24 30 30 30 30 30 Ultrasil 7000 90 90 90 90 90 GR ZnO RS 2 2 2 2 2 Edenor ST1 1 1 1 1 1 Vivatec 500 8.75 8.75 8.75 8.75 8.75 Rhenogran 2 2 2 2 2 DPG-80 Protector G 2 2 2 2 2 3108 Vulkanox 2 2 2 2 2 4020/LG Vulkanox 1.5 1.5 1.5 1.5 1.5 HS/LG Aktiplast ST 3.5 3.5 3.5 3.5 3.5 Si 363 10 — — — — Blend 1 — 30 — — — Blend 2 — — 30 — — Blend 3 — — — 30 — Blend 4 — — — — 30 2^(nd) stage Stage 1 batch 3^(rd) stage Stage 2 batch Perkacit 0.2 0.2 0.2 0.2 0.2 TBzTD Vulkacit 1.5 1.5 1.5 1.5 1.5 CZ/EG-C Sulphur 1.5 1.5 1.5 1.5 1.5

The polymer VSL 5025-2 is a solution-polymerized SBR copolymer from Bayer Ag having 25% by weight styrene content and 50% by weight vinyl fraction. The copolymer comprises 37.5 phr of TDAE oil, and has a Mooney viscosity (ML 1+4/100° C.) of 47.

The polymer Buna CB 24 is a cis-1,4-polybutadiene (Neodym type) from Bayer AG having at least 96% cis-1,4 content and a Mooney viscosity of 44±5.

Ultrasil 7000 GR is an easily dispersible silica from Evonik Industries AG with a BET surface area of 170 m²/g.

Vivatec 500 from Klaus Dahleke KG is used as TDAE oil, Vulkanox 4020 is 6PPD from Lanxess Europe GmbH & Co. KG, Vulkanox HS/LG is TMQ from Lanxess and Protektor G3108 is an antiozonant wax from Paramelt B.V., ZnO RS is ZnO from Arnsperger Chemikalien GmbH, EDENOR ST1 GS 2.0 is palmitic-stearic acid from Caldic Deutschland GmbH & Co. KG, and Aktiplast ST is a plasticizer from RheinChemie composed of a blend of hydrocarbons, Zn soaps and fillers. Rhenogran DGG-80 is composed of 80% of DPG on an EVA/EPDM carrier from RheinChemie and Vulkacit CZ is CBS from Lanxess Europe GmbH & Co. KG. Perkacit TBzTD (tetrabenzylthiuram disulphide) is a product of Flexsys N.V.

The rubber mixture is produced in three stages in an internal mixer according to Table 3.

TABLE 3 Stage 1 Settings Mixing assembly Werner & Pfleiderer GK 1,5E Rotation rate 80 min⁻¹ Ram pressure 5.5 bar Chamber temp. 80° C. Mixing process 0 to 0.5 min Buna VSL 5025-1 + Buna CB 24 0.5 min TMQ, 6PPD 0.5 to 1 min Mixing 1 to 2 min ½ Ultrasil 7000 GR, silane/silane-polymer blend, ZnO 2 min Purging and aeration 2 to 3 min ½ Ultrasil 7000 GR, Protector G3108, stearic acid, Vivatec 500, DPG, plasticizer 3 min Purging and aeration 3 to 4 min Mixing and discharge at 150°-160° C. Stage 2 Settings Mixing assembly As in stage 1 except: Rotation rate 90 min⁻¹ Mixing process 0 to 1 min Break-up of stage 1 batch 1 to 3 min Mixing at 155° C. 3 min Discharge Stage 3 Settings Mixing assembly As in stage 1 except Rotation rate 40 min⁻¹ Chamber temp. 50° C. Mixing process 0 to 0.5 min Stage 2 batch 0.5 to 2 min Accelerator and sulphur 2 min Discharge and form milled sheet on laboratory roll mill (Diameter 200 mm, length 450 mm, Roll temperature 50° C.) Homogenization: Form milled sheet for 20 s with roll gap of 3-4 mm, within next 40 s: cut the material and fold it over 3* towards the left and 3* towards the right, and roll the material 3* with narrow roll gap (3 mm) and then withdraw a milled sheet. Batch temp. <110° C.

The general process for the production of rubber mixtures and vulcanisates of these is described in “Rubber Technology Handbook”, W. Hofmann, Hanser Verlag 1994.

Technical testing takes place according to the test methods stated in Table 4.

TABLE 4 Physical testing Standard/conditions ML 1 + 4, 100° C. (3^(rd) stage) DIN 53523/3, ISO 667 Ring tensile test, 23° C. DIN 53504, ISO 37 Tensile stress values Dispersion coefficient See “Determination of (topography) dispersion coefficient” Viscoelastic properties, 0 and DIN 53 513, ISO 2856 60° C., 16 Hz, initial force 50 N and amplitude force 25 N Complexer module E* (MPa)

Determination of Dispersion Coefficient

The dispersion coefficient can be determined by a topographic method described in: “Entwicklung eines Verfahrens zur Charakterisierung der Füllstoffdispersion in Gummimischungen mittels einer Oberflächentopographie [Development of a surface-topography method for characterizing filler dispersion in vulcanized rubber mixtures]” A. Wehmeier; Degree thesis 1998 at the Münster University of Applied Sciences, Steinfurt site, in Chemical Engineering Department and “Filler dispersion Analysis by Topography Measurements” Degussa AG, Applied Technology Advanced Fillers, Technical Report TR 820.

The dispersion coefficient can also alternatively be determined by means of the DIAS method (optically) at the Deutsches Institut für Kautschuktechnologie in Hanover (see H. Geisler, DIK aktuell, 1^(st) Edition (1997) and Medalia, Rubber Age, April 1965).

The best achievable degree of dispersion is 100%, and accordingly the theoretically poorest would be 0%. Silicas with a dispersion coefficient above or equal to 90% can be classified as having high dispersibility (HD).

Explanation of the determination of dispersion coefficient by means of surface topography:

${{Dispersion}\mspace{14mu} {coefficient}} = {{100\mspace{11mu} \%} - {\frac{\begin{matrix} {\left( {{Total}\mspace{14mu} {areas}\mspace{14mu} {underlying}\mspace{14mu} {peaks}} \right) \cdot} \\ {10000\mspace{11mu} {\% \cdot {Medalia}}\mspace{14mu} {factor}} \end{matrix}}{{Filler}\mspace{14mu} {{volume} \cdot \left( {{total}\mspace{14mu} {area}\mspace{14mu} {tested}} \right)}}\%}}$ ${{Medalia}\mspace{14mu} {factor}} = \frac{\frac{{Filler}\mspace{14mu} {volume}}{100\mspace{11mu} \%} + 0.78}{2}$

dispersion coefficient in %

total areas underlying peaks (measure of roughness)

in mm²

filler volume in %

total area tested in mm²

Table 5 states the technical data for crude mixture and vulcanisate.

TABLE 5 Reference Reference Rubber mixture Rubber mixture Rubber mixture rubber rubber mixture I of the invention, II of the invention, III of the invention, mixture I II, comprising comprising blend 2 comprising blend 3 comprising blend 4 “in situ” blend 1 of the invention of the invention of the invention Results from crude mixture ML(1 + 4) at 114 129 102 96 107 100° C., 1^(st) stage [MU] Results from vulcanisate 100% Modulus 2.1 2.3 2.6 3.0 2.8 [MPa] 300% Modulus 11.9 not 12.5 13.3 12.8 [MPa] measurable MTS, 16 Hz, 14.8 14.0 20.1 33.5 30.8 initial force 50 N, amplitude force 25 N, 0° C. [MPa] MTS, 16 Hz, 7.5 7.9 9.1 10.9 11.3 initial force 50 N, amplitude force 25 N, 60° C. [MPa] Dispersion 1.5 7.0 1.0 2.0 1.7 (topography) [%]

In comparison with the isomolar in-situ mixture or mercaptosilane-polymer blend with polyamide, the rubber mixtures comprising the mercaptosilane-polymer blends of the invention exhibit improved processing performance (lower Mooney viscosities in the 1^(st) mixing stage), improved reinforcement performance (higher moduli), improved dynamic stiffness and excellent dispersion. 

1: A mercaptosilane-polymer blend, comprising at least one mercaptosilane of the general formula I:

wherein R¹ is an alkyl polyether group —O—(R⁵—O)_(m)—R⁶, where R⁵ is identical or different and is a branched or unbranched, saturated or unsaturated, aliphatic divalent C1-C30 hydrocarbon group, m is on average from 1 to 30, and R⁶ comprises at least 1 C atom and is an unsubstituted or substituted, branched or unbranched monovalent alkyl, alkenyl, aryl or aralkyl group, R² is identical or different and is an R¹, C1-C12-alkyl or R⁷O group, where R⁷ is H, methyl, ethyl, propyl, C9-C30 branched or unbranched monovalent alkyl, alkenyl, aryl, or aralkyl group or (R⁸)₃Si group, where R⁸ is C1-C30 branched or unbranched alkyl or alkenyl group, R³ is a branched or unbranched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic/aromatic divalent C1-C30 hydrocarbon group, and R⁴ is H, CN or (C═O)—R⁹, where R⁹ is a branched or unbranched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic/aromatic monovalent C1-C30 hydrocarbon group; and at least one polymer selected from the group consisting of polypropylene, polyethylene, ethylene-vinyl acetate and mixtures thereof. 2: The mercaptosilane-polymer blend of claim 1, comprising a mixture of mercaptosilanes of the general formula I. 3: The mercaptosilane-polymer blend of claim 2, wherein the mixture of mercaptosilanes of the general formula (I) comprises

4: The mercaptosilane-polymer blend of claim 1, wherein the at least one mercaptosilane of the general formula I further comprises products of the hydrolysis and/or condensation of the mercaptosilanes of the general formula I. 5: The mercaptosilane-polymer blend of claim 1, wherein a molar mass of the polymer is from 50 000-1 000 000 g/mol. 6: The mercaptosilane-polymer blend of claim 1, wherein a bulk density of the polymer is from 80-150 kg/m³. 7: A process for producing the mercaptosilane-polymer blend of claim 1, the process comprising mixing the at least one mercaptosilane of the general formula I with the at least one polymer selected from the group consisting of polypropylene, polyethylene, ethylene-vinyl acetate and mixtures thereof. 8: The process of claim 7, wherein the mixing occurs with a ploughshare mixer. 9: A rubber mixture, comprising the mercaptosilane-polymer blend of claim
 1. 10: A rubber mixture, comprising (A) at least one rubber, (B) at least one filler, and (C) the at least one mercaptosilane-polymer blend of claim
 1. 11: A process for producing the rubber mixture of claim 10, the process comprising mixing the at least one rubber, the at least one filler, the at least one mercaptosilane-polymer blend, and optionally at least one other rubber auxiliary in a mixing assembly. 12: A moulding produced from the mercaptosilane-polymer blend of claim
 1. 13: An article produced from the mercaptosilane-polymer blend of claim 1, the article selected from the group consisting of a tire, a tire tread, a cable sheathing, a hose, a drive belt, a conveyor belt, a roll covering, a shoe sole, a sealing ring, and a damping elements. 